Effects of amine-based covalent organic framework on platinum electrocatalyst performance towards hydrogen evolution reaction

Performance of electrocatalyst in an aqueous electrolyte is greatly influenced by the structure of electrolyte-electrocatalyst interface. Regulating mass transfer is important in controlling surface reactions to alter the overall reaction kinetics. Thus, modification of interfacial structures is an effective approach to improving the electrocatalytic performance. In this paper, we report the use of functionalized amine-based covalent organic frameworks (COFs) as the modifier of electrocatalytic properties by facilitating the proton transfer of hydrogen evolution reaction (HER) in an acidic medium. Results from the electrochemical solid-liquid interface (ESLI)-based density functional theory (DFT) calculations suggest that functionalized COFs increase the local hydrogen concentration at the COF-electrocatalyst interface. Our simulation data indicates the enhancement in HER activity is achieved partially through the protonation site of the secondary amine of the COF on electrode surface, suggesting a new mode of controlling interfacial proton transfer for improving the HER kinetics.